Process for the extraction of the albumino-caseins of vegetable origin and for the separation of such albumino-caseins from amylaceous matter



Patented Apr. 22,- 1930 PATENT OFFICE HENRI BEAUFOUR, OF BEAUVAIS, FRANCE rnooEss FOR THE EXTRACTION OF THE ALBUMINO-CASEINS or VEGETABLE ORIGIN AND FOR THE SEPARATION MATTER OF SUCH ALBUMINO-CASEINS FROM AMYLACEOUS No Drawing. Application filed October 11, 1926, Serial a... 141,031, and in France October 23, 1925.

My invention relates to the obtainment of the albumino-caseins of vegetable origin, and. the separation of the same from amylaceous substances, the resulting products having 5 'physico-chemical characteristics resembling those of the albumino-caseins of animal origin and chiefly in the fact that they are soluble in the-alkalies and are coagulated by heat, in view of their utilization for all industrial purposes for which the albumens k same, of sodium chloride in the state of more and caseins of animal origin are now employed.

The said invention consists essentially in v the treatment of cereals ortheir germs, or of oleaginous grain or seeds from which the oil has been optionally removed, soja arachis' such as leguminous grain or seeds, oil nuts or the like in a suitably ground state, or their oil cake, by means of a solution (of the proper strength) of a chloride of the alkalies,

alkali earths, or of a mixture of such chlorides; I

It consists chiefly in the utilization, as the chloride serving to dissolve the albuminocaseins contained in plants or portions of the or less concentrated sea water. In particular, I may commence the treatment by causing the substance to swell in the concentrated salt solution.

The invention further relates to the treatment by suitable bases andchiefly by lime or other alkali earth hydrates, before or after the use of the salt solution, and by the said I treatment I am enabled'to purify the substance to a certain extent and to obtain a casein which can be coagulated with a partic'-.

ular facility. p o

It further relates to the washin of the coagulated substance by water. w ich has been given a certain ionizing power. I

.My invention also comprises, as new manufactured products, the albumino-caseins obtained by the aforesaid process, which are free from alkali-albumens, starch, fatty mat: ter and soaps, and whose physico-chemical characteristics are very near those of the albumino-caseins of'animal origin and which are particularly well adapted for coagulation by heat, so that they may be utilized as Substitutes for the albumens and caseinsofanimal origin for all industrial purposes for which these latter are employed.

In particular, for the extraction of the aforesaid albumino-caseins from cereals or their germs, or from oleaginous grain or seeds from which the oilhas .been optionally removed, or from their oil cake, I may proceed as follows.

The said material, which is suitably ground, is treated with a solution containing 50-100 grams per liter of water of an al- 1 kaline chloride (of'potassium ammonium or sodium), an alkaline earth chloride (of calcium orbarlum) or an earth chloride (of magnesium) in concentrated solution, of 3 per starch. The resulting 'albuminous solution,

which is free from starch and fatty matter, and is optionally treated with .an alkali or and alkali earth hydrate in slight excess in order to precipitate the inert substances dissolved in the chloride water, is separated from the insoluble substances which are not dissolved'or are precipitated (such as celluloses, insoluble mineral substances, or the like) by adequate mechanical means, and is then treated by an organic or an inorganic acid, by a salt of copper, lead or magnesium, or by rennet. (labferment), or by a like sub-- stance adapted to coagulate the casein, in

order to precipitate the albuminoid matter.

The optimumconditions of coagulation will depend upon the degree of ironization of the albuminous-solution. The casein is then collected either by settling,"by filtering or' by centrifugal treatment; itis washed with ionized water to remove the glucose substances, the mmeral salts, or any ac1d reaction,

and is then dried at a temperature below 50 degrees C. in a strong current of air.

The caseo-albumen may also be obtained from its chlorinated solution by-coagulation 6 (with the optional addition of lime), but in this case, I prefer to bring it preliminarily to a suitable state of ionization, as will be hereinafter set forth.

The addition water not containing chlo- 10 rides will also precipitate the caseo-albumen. i l-process which offered excellent results in'p'ractice is given in detail as follows:

The material under treatment, such as oil cake from peanuts from which the oil has been extracted by a first operation, is suitably :ground and is then worked up into a soft paste witjn natural sea water containing 3 per cent of NaCl or a larger percentage of-salt, or with a5 per cent solution of sea salt or rock salt, .20 0! with-a 5 per cent solution of calcium chloride,-and is-tbenallowed to stand for the time necessary for the swelling of the proteic substances. v

The material can treated with sea water in the naturalstate or inure orless concentrated, or by water contraining 5 per cent-ofsalt, or containing calcium ehloride either in the hot or cold state, in-the proper proportion. so I It bas-been feund that the proportion af- -fording1 good results is 10 parts of sea water, Ao'r oft-3., 1' cent salt-solution, for 1 part of theoil employed. 1

I Loperate by maceration or by working up,

=orbysystematic lixiviation, or by like methfor theexhaustion-of the material, and eta temperature below degrees C.

1 thus'obtain an albuminous solution which may-thenhe treated with lime, in the state 14'0 43f milk of lime, and this affords a pre- 'cipitateof insoluble substances; the resultiseluti onhas a greenish-yellow colour. The available caseinates remain in solution,

the, precipitate chiefly contains the nu- 45 cl'eiuates, glutens and various other inert and indeterminate substances.

This operation serves to free the solution from all prejudicial substances, and I can ithus-obtaiaueven in the cold state, a suitable p90 easeinwhich can be employed in the. various industries such as the manufacture of plastic1 substances by agglomeration, the manufaiit'ure of casein paints and adhesive sub- 'stfinceabarytai paper, andsizing, or for the fi'xir'1"gio; colours, or the like.

It should be noted that the lime treatment might also be effected before the caseo-alhuman is dissolved in the chloride solution. 1

' My experience seems to show that in this case the lime treatment will peptize the albumi? 'neids *while facilitating their subsequent "swelling, but that in-this event the inert mat- :ter willbe insoluble in the chlorine salts. I

s-The solution resulting from the 'sucoes ,sivetreatments with chlorides and with lime,

very high speed. The solution is of a pale yellow colour, and should be quite clear.

As above stated, the caseo-albumen may be precipitated by any of the usual reagents,

with success, even in the cold state:

The acetic, hydrochloric and sulphurous acids, solutions of sulphides, sulphites, hisulphites or hydrosulphites, solutions of the alums, a solution of sulphate of aluminium, or suitable mixtures of'such substances, or the like. I

Ihave observed that the coagulation is a maximum when the ionizingpower attains a determined value for a given material under treatment, and such values will depend upon the nature of the said substance. The critical ionizing value (which is near the isoe1ec p tric point) for the treatment of the earth nut then'be advantageously or peanut) material, is Ph= 5L2 approximately. This will allow of the exact measurement of the quantity ofcoagulating agents to be added to thersolution for the obtainment of a complete precipitation. Further, it is simply necessary to observe the ionizi-ng power of the solution at all times by means of'a suitable. re ent, for instance methyl red, in order to fin whether the coagulating operationhasbeen completed.

The resulting coagulated substance is then separated from its mother liquor by suitable means. It is not to be Washed withall kinds .of water, but (preferably) with water whose ionizing power has been brought to the critical value corres onding to the raw material employed. In t iismanner there is no danger i that the coagulated substance will be re-dissolved or will become swelled durin'g the washing. H r

After the curdy material has been separated and disintegrated, it is driedand ground by the known methods.

As an accessory treatment, the 'caseo-al- -bumen 'which is precipitated by any of the aforesaid methods, maybe bleached by'hyvdroxyl or a perborate or persulphate or by Y sulphurous orfhy drosulphurous acid orin other .cases,.the.solution maybe treated with decolouring a ents before it is precipitated.- The insolub e residues from the extraction urposes andchiefly for the extraction'of and I chiefly employ the following substances of-the caseo-albumens maybe suitably dried are atty subetaliceafaswell asfor the manufacture of starch.

' ,The vcj'aseo albumen of vegetable origin gwhi'chlobtain b my. said process will conetitute 'a'new st'i stance which differs from the caseinsof vegetable origin'hi'therto v as well as from casein of animal This casem' is free from alkali-a1- slightly bro when it is well of an acid or a base,

'termined value for each kind of bumens, starch,-fatty matter and soaps; After drymg, and when not decoloured, it has the appearance of a more or less translucent and horny substance, which is very hard dried.- 'Its colour will depend upon the state of purity of the raw material and chiefly upon the method of operation, and is generally a more or less pronounced yellow, but may, attain an amber or greenish or blackish yellow, or even a mahogany red. With the earth nut (or peanut), a product of good quality will show a brilliant fracture. The appearance of the fracture resembles that of rosin.

In the powdered appearance of a white powder having a wnish or amber hue, or otherwise msh. In the state of small grains, it resembles sea san Analysis of the earth nut or peanut casein inthe state of flour shows that it may contain upwards of 10 per cent of water, less than 3 per cent of ash and about 14 per cent of nitrogen, also sulphur and phosphorus.

When this casein is redissolved in anexcess it attains the maximum coagulation when the ionization has a deraw material, and depending upon the said material. peanut, this ionizing For the earth nut or power is about 5, 2, it being estimated in practice by the use of methyl red.

' may be utilized for the bleaching of the said or hydr'osulphurous acid.

alumino casein by a solution 0 The vegetable caseins and albumens which are obtained by vmy said process can be utilized for industrial purposes in the same manner as the'animalcaseins and albumens, and may be dustries utilizing such caseins and albumens whether natural or hydrolyzed, and chiefly inthe manufacture of baryta paper, adhesive substances and paint based upon casein, sizfor textilefabrics, agglomerated plastic su tances, for the fixingof colours, and for other uses.

Further, the .new manufactured product which is obtained in accordance with my said invention may be utilizedin the manufacture of alimentary, pharmaceutic and dietetic products.

On the other hand, the solubilizing of the vegetable caseins by the neutral chlorides have a very interesting field of use in the purifying of starch. A

Having particularly described my said mvention and the manner m which the sameis to be performed, claim is: 1. A process for the manufacture of casein from vegetable substances comlprising treating the raw material by an a ali chloride, purifying the product of this first step by the addition of lime, separating the insoluble declare that what I state, this casein has the- 's property substituted therefor in all mreatment with fiected tothe degree that Ph= 5,2. orthe manufacture of casein the remaining acid, the coagulafrom vegetable substances comprismg washing the coagulated casem with has been brought to the critspondin ionizing ical value corre employed, for instance nut;

sulphurous power water whose to the raw material h=5,2 forthe pea- HENRIBEAUFOUR.

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